CN112662261A - Self-cleaning road marking paint and preparation method thereof - Google Patents
Self-cleaning road marking paint and preparation method thereof Download PDFInfo
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Abstract
A self-cleaning road marking paint is a mixture obtained by mixing 50-150 parts by mass of modified acrylic resin, 0.1-2 parts by mass of an accelerator, 1-10 parts by mass of inert oil and 10-50 parts by mass of a low-boiling point and low-surface tension solvent to form a component A, mixing 50-150 parts by mass of modified acrylic resin, 1-10 parts by mass of a curing agent, 1-10 parts by mass of inert oil and 10-50 parts by mass of a low-boiling point and low-surface tension solvent to form a component B, wherein the modified acrylic resin is prepared by dissolving solid acrylic resin in active monomers of methyl methacrylate, butyl acrylate and hydroxypropyl methacrylate as a dispersion medium, adding an inorganic filler and pigment nano titanium dioxide, and modifying the inorganic filler and the nano titanium dioxide by using a silane coupling agent. The coating can realize the continuous and long-term self-cleaning effect of the road marking on the premise of not increasing the surface smoothness of the road marking.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to a road marking coating, in particular to a road marking coating with a self-cleaning function and a preparation method of the road marking coating.
Background
Road markings are an important component of road safety. Because it has the traffic guide function, consequently, the observation effect of road marking will influence driver's driving experience to influence the security. If the road marked lines are easy to be dirty, the indicating effect of the marked lines can be suddenly and rapidly reduced in a short time, and the guiding function is reduced, so that potential safety hazards are caused.
In order to solve the problem that road markings are easy to dirty, the conventional solution is to improve the anti-fouling effect of the marking paint by improving the surface smoothness of a coating layer of the marking paint.
However, this approach still has two problems: on one hand, the surface smoothness is improved, so that the surface anti-sliding coefficient of the road marking is reduced, the braking distance of an automobile is prolonged, or pedestrians slide to the automobile, and potential safety hazards are increased; on the other hand, the anti-fouling effect is related to the surface structure, and along with the increase of the service time of the road marking, the surface structure is worn and damaged, so that the road marking is bound to lose the anti-fouling effect and become easy to foul.
Therefore, the invention provides the marking paint which has low surface smoothness and can continuously resist pollution, and the problems in the industry can be effectively solved.
Disclosure of Invention
The invention aims to provide a self-cleaning road marking paint and a preparation method thereof, so as to improve the anti-fouling capability of the road marking paint on the premise of not increasing the surface smoothness of the road marking.
The self-cleaning road marking paint consists of 1 part by mass of a component A and 1-2 parts by mass of a component B which are independently packaged.
Wherein the component A is formed by mixing 50-150 parts by mass of modified acrylic resin, 0.1-2 parts by mass of accelerator, 1-10 parts by mass of inert oil and 10-50 parts by mass of low-boiling-point and low-surface-tension solvent;
the component B is formed by mixing 50-150 parts by mass of modified acrylic resin, 1-10 parts by mass of curing agent, 1-10 parts by mass of inert oil and 10-50 parts by mass of low-boiling-point and low-surface-tension solvent;
the modified acrylic resin is a mixture obtained by dissolving solid acrylic resin in active monomers of methyl methacrylate, butyl acrylate and hydroxypropyl methacrylate as a dispersion medium, adding an inorganic filler and pigment nano titanium dioxide, and modifying the inorganic filler and the nano titanium dioxide by using a silane coupling agent.
Further, the dispersion medium is composed of 50-70 parts by mass of methyl methacrylate, 20-30 parts by mass of butyl acrylate, 10-20 parts by mass of hydroxypropyl methacrylate and 70-100 parts by mass of solid acrylic resin.
Further, the adding amount of the inorganic filler is 100-200% of the mass of the dispersion medium.
Furthermore, the addition amount of the pigment nano titanium dioxide is 10-30% of the mass of the dispersion medium.
The acrylic resin is a core component for curing the road marking paint, and the acrylic resin is used as a dispersing medium for modifying the inorganic filler and the nano titanium dioxide by taking the characteristic of fluidity of the acrylic resin, dispersing the inorganic filler and the nano titanium dioxide in the acrylic resin, and modifying the acrylic resin by using the silane coupling agent, so that the inorganic filler and the nano titanium dioxide are fully dispersed in the resin, and the agglomeration phenomenon of the inorganic filler and the nano titanium dioxide is avoided. The inorganic filler, the nano titanium dioxide and resin molecules are distributed in a more balanced state, more uniform nano hole structures can be formed in the subsequent curing process of the resin, and the hydrophobic effect of the road marking coating is improved. Moreover, the invention also avoids the modification of the inorganic filler and the nano titanium dioxide independently, saves the drying link of the inorganic filler and the nano titanium dioxide, simplifies the operation steps and saves the time and the energy consumption.
In the modified acrylic resin, the solid acrylic resin is a polymer obtained by copolymerization of at least one or more of methyl (meth) acrylate and butyl (meth) acrylate, hydroxypropyl (meth) acrylate or styrene.
The inorganic filler is an inorganic material containing hydroxyl functional groups, and comprises but is not limited to at least one of porous silica microspheres, silica micropowder, apatite micropowder, alumina micropowder, hollow glass microspheres and the like.
Further, the present invention preferably employs porous silica microspheres as the inorganic filler.
Furthermore, the silane coupling agent of the invention contains C in the molecular structurenH2n+1(n is more than or equal to 10) various alkyl silane coupling agents of molecular chain segments or C contained in molecular structurenF2n+1(n is more than or equal to 3) a fluorosilane coupling agent with molecular chain segments.
The silane coupling agent is grafted on the inorganic filler and the nano titanium dioxide, so that the surface free energy of the inorganic filler and the nano titanium dioxide can be obviously reduced. The fluorine element has the strongest electronegativity, low atom polarizability, large C-F bond energy, and spiral distribution of fluorine atoms along the carbon bond, thereby having shielding effect and small intermolecular force, and being capable of effectively reducing the surface free energy of the coating, so that the fluorine silane coupling agent is preferably used in the invention.
The accelerator added in the component A and the curing agent added in the component B are the curing agent and the accelerator which can initiate acrylic polymerization reaction at normal temperature after being mixed.
Specifically, the accelerator includes, but is not limited to, at least one of N, N-dimethylaniline, N-dimethyl-p-toluidine; the curing agent includes but is not limited to at least one of cyclohexanone peroxide, methyl ethyl ketone peroxide and benzoyl peroxide.
Furthermore, according to the invention, a certain proportion of inert oil is added into the component A and the component B for adsorbing nano holes formed by the modified inorganic filler and the nano titanium dioxide during curing, so that the hydrophobic property of the coating is further improved. The inert oil includes but is not limited to at least one of simethicone, tung oil, castor oil and linseed oil.
The invention also adds a certain proportion of low boiling point and low surface tension solvent into the component A and the component B for coating the modified inorganic filler and the nano titanium dioxide to form a microsphere structure. In the subsequent resin curing process, the microsphere structures are mutually adhered to form nano porous structures on the surface and inside of the coating, and the nano porous structures are matched with the modified inorganic filler and the nano titanium dioxide exposed outside the resin, so that the super-hydrophobic effect is realized.
The low-boiling point and low-surface tension solvent includes but is not limited to at least one of n-hexane, methanol, ethanol and low-boiling point fluorinated liquid. More preferably, the low boiling, low surface tension solvent is a low boiling fluorinated liquid.
Therefore, the pigment and the filler containing hydroxyl are subjected to coupling modification to enable the pigment and the filler to have hydrophobic performance, a small amount of low-tension solvent is added into the coating, a nano-convex porous structure can be formed along with solvent shrinkage during coating curing, the structure is nano-scale, so that hydrophobicity can be shown, the structure is hydrophobic from inside to outside due to the modification of the pigment and the filler, the inert oil is added to enable the inert oil to be easily adsorbed in the holes, on one hand, the filling protection effect on the holes is achieved, on the other hand, the inert oil also has low surface tension, the hydrophobic area of the coating can be enlarged, and therefore the hydrophobic effect is improved.
The preparation method of the self-cleaning road marking paint is not particularly limited, and the self-cleaning road marking paint can be prepared by various conventional mixing methods which can uniformly mix the component A and the component B which form the self-cleaning road marking paint.
Specifically, adding 0.1-2 parts by mass of an accelerator, 1-10 parts by mass of an inert oil and 10-50 parts by mass of a low-boiling point and low-surface tension solvent into 50-150 parts by mass of modified acrylic resin, stirring and mixing for 0.5-1 hour at a speed of 400-900 r/min, and sealing to obtain a component A of the self-cleaning road marking paint; adding 1-10 parts by mass of curing agent, 1-10 parts by mass of inert oil and 10-50 parts by mass of low-boiling point and low-surface tension solvent into 50-150 parts by mass of modified acrylic resin, stirring and mixing for 0.5-1 hour at 400-900 r/min, and sealing to obtain the component B of the self-cleaning road marking paint.
The modified acrylic resin is prepared by the following method: uniformly mixing 50-70 parts by mass of methyl methacrylate, 20-30 parts by mass of butyl acrylate and 10-20 parts by mass of hydroxypropyl methacrylate, adding 70-100 parts by mass of solid acrylic resin, uniformly dissolving to obtain a dispersion medium, adding an inorganic filler accounting for 100-200% of the mass of the dispersion medium and pigment nano titanium dioxide accounting for 10-30% of the mass of the dispersion medium, uniformly dispersing, adding 1-10 parts by mass of a silane coupling agent, heating to 60-80 ℃, stirring, refluxing and reacting for 1-2 hours to obtain the modified acrylic resin.
When in use, the component A and the component B are uniformly mixed according to the mass fraction to initiate free radical reaction, and then the self-cleaning road marking paint can be prepared.
After the component A and the component B are mixed, the curing agent generates free radicals under the action of the accelerator, wherein the component containing the active double bond can generate free radical polymerization, so that a cross-linked network is formed, and the curing film is formed. In actual construction, the two components are separately atomized and mixed on a floor base by an apparatus having a double nozzle, thereby initiating radical polymerization.
The self-cleaning road marking paint provided by the invention can be applied to various base materials such as asphalt concrete, cement concrete and the like, has the characteristics of no toxicity, no harm and environmental friendliness, can be cured at a low temperature, and can realize quick traffic release.
The self-cleaning road marking coating disclosed by the invention is high in curing efficiency and high in speed, can be cured under a low-temperature condition in winter, and has no reduction in application places and higher applicability compared with the traditional MMA marking.
In addition, the carbon long chain with strong hydrophobic effect is introduced into the coating molecules of the road marking coating through silane hydrolysis, so that the pigment and the filler in the coating have lower free energy, the coating is subjected to shrinkage molding in the curing process by a low-boiling-point solvent to form a porous nano-pore structure, the rough structures of the inner part and the outer part of the coating are increased, and a nano-convex structure can be formed on the surface of the coating, so that the coating has excellent hydrophobic effect. Meanwhile, the inert oil added in the coating can fill the nano holes of the pigment and the filler under the action of intermolecular force and chemical bond force, so that the low free energy area of the surface of the coating is enlarged, the hydrophobic effect is enhanced, the integral hydrophobic characteristic is constructed, and the continuous and long-term self-cleaning effect is realized.
The road marking prepared by the self-cleaning road marking coating has lower surface tension and is not easy to be stained with dust, and water has larger contact angle on the surface of the marking, so that the free flow of water drops on the surface can be realized, thereby easily taking away the dust on the surface of the coating, realizing the self-cleaning effect.
Drawings
FIG. 1 is a scanning electron micrograph of a sample of the self-cleaning road marking coating of example 1.
FIG. 2 is a graph showing the effect of example 1 on the formation of water droplets on the surface of a sample of a self-cleaning road marking coating.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings and examples. The following examples are only for more clearly illustrating the technical solutions of the present invention so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the scope of the present invention.
In the present invention, the terms such as "upper", "lower", "left", "right" and "middle" are used for clarity of description only, and are not used to limit the scope of the present invention, and the relative relationship changes or adjustments may be made without substantial technical changes and modifications.
The raw materials used in the examples of the present invention are not particularly limited in terms of source unless otherwise specified. Even materials purchased on the market can be prepared according to conventional methods well known to those skilled in the art.
The names and the short names of the process and the equipment adopted by the invention belong to the conventional names in the field, each name is quite clear and definite in the field of related application, and a person skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names.
Example 1.
Weighing 60g of methyl methacrylate, 30g of butyl acrylate, 20g of hydroxypropyl methacrylate and 80g of Liaoning tricycloTMA-02 solid acrylic resin, 180g of porous silica microspheres and 20g of nano titanium dioxide (1000 meshes) are sequentially added into a reaction vessel, stirred for 30min, then 2g of perfluorodecyl trimethoxy silane coupling agent is added, and the mixture is heated to 80 ℃ under continuous stirring for reflux reaction for 1 hour to prepare the modified acrylic resin.
100g of modified acrylic resin is taken, and 0.2g N, N-dimethylaniline, 10g of dimethyl silicone oil and 20g of 3M are addedTM7100 stirring the fluorinated solution at 800r/min for 1 hour, discharging, sealing and storing to obtain the component A of the self-cleaning road marking paint.
Taking 100g of modified acrylic resin, adding 3g of benzoyl peroxide and 10g of dimethyl siliconOil, 20g 3MTM7100 stirring the fluorinated solution at 800r/min for 1 hour, discharging, sealing and storing to obtain the component B of the self-cleaning road marking paint.
And (3) mixing the component A and the component B according to the weight ratio of 1:1, stirring for 1min to uniformly mix, carrying out blade coating on tinplate by using a 600-micron coater, and obtaining a self-cleaning road marking coating sample after complete reaction.
FIG. 1 shows a scanning electron micrograph of a coated sample. It can be observed from the figure that after the coating is cured, a porous structure is formed on the surface layer and inside the coating, and a small amount of inert oil is adsorbed in the pores (dark areas inside the pores).
These porous structures thus increase the roughness of the coating surface, the rough surface structure being the basis for the formation of superhydrophobicity. In addition, the adsorbed inert oil can protect the hole structure, can expand the low free energy area, and further improves the hydrophobic effect of the coating.
The effect shown in FIG. 2 was observed by slowly dropping several drops of water on the coating surface by sucking water with a dropper, which indicates that the coating surface was hydrophobic and the drops were in the form of water beads and did not wet the coating surface.
Example 2.
Weighing 50g of methyl methacrylate, 20g of butyl acrylate, 10g of hydroxypropyl methacrylate and 100g of Liaoning tricyclicTMA-04 solid acrylic resin, 110g hollow glass beads and 10g nano titanium dioxide (1000 meshes) are sequentially added into a reaction vessel, stirred for 30min, then 10g dodecyl trimethoxy silane coupling agent is added, and the mixture is heated to 60 ℃ under continuous stirring for reflux reaction for 2 hours to prepare the modified acrylic resin.
And (3) taking 100g of modified acrylic resin, adding 1g N, N-dimethyl-p-toluidine, 8g of tung oil and 30g of N-hexane, stirring for 0.5 hour at the speed of 800r/min, discharging, sealing and storing to obtain the component A of the self-cleaning road marking paint.
And (3) taking 100g of modified acrylic resin, adding 5g of benzoyl peroxide, 8g of tung oil and 30g of n-hexane, stirring for 0.5 hour at the speed of 800r/min, discharging, sealing and storing to obtain the component B of the self-cleaning road marking paint.
And (3) mixing the component A and the component B according to the weight ratio of 1:1, stirring for 1min to uniformly mix, carrying out blade coating on tinplate by using a 600-micron coater, and obtaining a self-cleaning road marking coating sample after complete reaction.
Comparative example 1.
MMA road marking paint was prepared according to "road marking materials and applications" (Do Li Min, Zheng Home, He Yong. people traffic Press [ M ]: Beijing, 2005: 85-95.).
40g of solid acrylic resin Degaroute is taken®660. 2g of plasticizer Degaroute®W3, 30g of superfine calcium carbonate (1000 meshes), 17.5g of superfine quartz powder (1000 meshes) and 10g of pigment R902, and the components are uniformly mixed to form the component A.
40g of solid acrylic resin Degaroute is taken®662. 2g of plasticizer Degaroute®W3, 30g of superfine calcium carbonate (1000 meshes), 17.5g of superfine quartz powder (1000 meshes) and 10g of pigment R902, and the components are uniformly mixed to form the component B.
And (3) mixing the component A and the component B according to the weight ratio of 1:1, adding 4g of benzoyl peroxide, stirring for 1min to uniformly mix, carrying out blade coating on tinplate by using a 600-micron coater, and obtaining an MMA road marking sample after the reaction is completed.
The coating film performance of the self-cleaning road marking coating samples and the MMA road marking samples in the examples 1 and 2 are respectively tested.
Wherein, the indexes of tensile strength and elongation at break are carried out according to the GB/T2567-2008 method, the indexes of glossiness are tested according to the methods in GB 1743-1979(1989), the test of the anti-slip coefficient is referred to the JT/T712-2008 standard method, and the test of the contact angle is carried out according to the GB/T30693-2014 method.
As can be seen from the comparison of the test results of the comparative example and the test results of the example, the test sample prepared by the self-cleaning road marking paint of the invention has tensile strength and elongation at break which are closer to those of the test sample prepared by the traditional MMA road marking paint, and the physical properties are closer, which means that the using effects of the two are equivalent.
Meanwhile, the self-cleaning marking sample has low glossiness (less than 10GU) and belongs to a low-gloss coating, while the traditional MMA road marking is more than 10GU and belongs to a medium-gloss coating. Correspondingly, the anti-skid coefficient of the self-cleaning marking sample can be increased to about 30, and the traditional MMA road marking is only 11, which shows that the anti-skid effect of the self-cleaning road marking coating is improved.
In addition, the contact angles of water and oil on the surface of the self-cleaning marking sample are obviously higher than those of the traditional MMA road marking, so that the self-cleaning marking sample has a better anti-fouling effect. Even if the surface of the coating is polished, the coating sample still has a higher water-oil contact angle, which shows that the coating also has a self-cleaning effect and a more durable self-cleaning effect.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Claims (10)
1. A self-cleaning road marking paint is composed of 1 part by mass of a component A and 1-2 parts by mass of a component B which are independently packaged, wherein:
the component A is formed by mixing 50-150 parts by mass of modified acrylic resin, 0.1-2 parts by mass of an accelerant, 1-10 parts by mass of inert oil and 10-50 parts by mass of a low-boiling-point and low-surface-tension solvent;
the component B is formed by mixing 50-150 parts by mass of modified acrylic resin, 1-10 parts by mass of curing agent, 1-10 parts by mass of inert oil and 10-50 parts by mass of low-boiling-point and low-surface-tension solvent;
the modified acrylic resin is a mixture obtained by dissolving solid acrylic resin in active monomers of methyl methacrylate, butyl acrylate and hydroxypropyl methacrylate as a dispersion medium, adding an inorganic filler and pigment nano titanium dioxide, and modifying the inorganic filler and the nano titanium dioxide by using a silane coupling agent.
2. The self-cleaning road marking paint as claimed in claim 1, wherein the dispersion medium is composed of 50-70 parts by mass of methyl methacrylate, 20-30 parts by mass of butyl acrylate, 10-20 parts by mass of hydroxypropyl methacrylate and 70-100 parts by mass of solid acrylic resin.
3. The self-cleaning road marking paint as claimed in claim 1, wherein the inorganic filler is added in an amount of 100-200% by mass of the dispersion medium, and the pigment nano titanium dioxide is added in an amount of 10-30% by mass of the dispersion medium.
4. The self-cleaning road marking paint of claim 1, wherein the solid acrylic resin is a polymer obtained by copolymerization of at least one or more of methyl (meth) acrylate, butyl (meth) acrylate, hydroxypropyl (meth) acrylate, or styrene.
5. The self-cleaning road marking paint of claim 1, wherein the inorganic filler is at least one of porous silica microspheres, fine silica powder, fine apatite powder, fine alumina powder, and hollow glass beads.
6. The self-cleaning road marking paint of claim 1, wherein the silane coupling agent is a silane coupling agent having a molecular structure containing CnH2n+1(n is more than or equal to 10) alkyl silane coupling agent with molecular chain segment or C contained in molecular structurenF2n+1(n is more than or equal to 3) a fluorosilane coupling agent with molecular chain segments.
7. The self-cleaning pavement marking paint of claim 1, wherein the accelerator is N, N-dimethylaniline or N, N-dimethyl-p-toluidine and the curing agent is cyclohexanone peroxide, methyl ethyl ketone peroxide or benzoyl peroxide.
8. A self-cleaning road marking paint as claimed in claim 1, wherein the inert oil is at least one of dimethicone, tung oil, castor oil, linseed oil.
9. The self-cleaning road marking paint of claim 1, wherein the low-boiling, low-surface tension solvent is at least one of n-hexane, methanol, ethanol, low-boiling fluorinated liquid.
10. A preparation method of a self-cleaning road marking paint comprises the steps of uniformly mixing 50-70 parts by mass of methyl methacrylate, 20-30 parts by mass of butyl acrylate and 10-20 parts by mass of hydroxypropyl methacrylate, adding 70-100 parts by mass of solid acrylic resin, uniformly dissolving to obtain a dispersion medium, adding an inorganic filler accounting for 100-200% of the mass of the dispersion medium and pigment nano titanium dioxide accounting for 10-30% of the mass of the dispersion medium, uniformly dispersing, adding 1-10 parts by mass of a silane coupling agent, heating to 60-80 ℃, stirring, refluxing and reacting for 1-2 hours to obtain modified acrylic resin;
adding 0.1-2 parts by mass of an accelerator, 1-10 parts by mass of inert oil and 10-50 parts by mass of a low-boiling point and low-surface tension solvent into 50-150 parts by mass of modified acrylic resin, stirring and mixing for 0.5-1 hour at a speed of 400-900 r/min, and sealing to obtain a component A of the self-cleaning road marking paint;
adding 1-10 parts by mass of curing agent, 1-10 parts by mass of inert oil and 10-50 parts by mass of low-boiling point and low-surface tension solvent into 50-150 parts by mass of modified acrylic resin, stirring and mixing for 0.5-1 hour at 400-900 r/min, and sealing to obtain the component B of the self-cleaning road marking paint.
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